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Effect of MnO2 doped on physical, structure and optical properties of zinc silicate glasses from waste rice husk ash 1 3 4 5 6 7 8 9 10 1 2 13 14 15 16 17 18 19 20 21 22 23 24 25 2 6 45 46 47 48 49 50[.]

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5

6

7 Ali Jabbar Abed Al-Nidawia, Khamirul Amin Matoria,b,⇑, Azmi Zakariaa, Mohd Hafiz Mohd Zaida,b

Department of Physics, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia

Materials Synthesis and Characterization Laboratory, Institute of Advanced Technology, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia

10

1 2 a r t i c l e i n f o

13 Article history:

14 Received 26 January 2017

15 Received in revised form 14 February 2017

16 Accepted 15 February 2017

17 Available online xxxx

18 Keywords:

19 Rice husk

20 Manganese dioxide

21 Glass

22 Zinc silicate

23 Sintering

24 Optical properties

25

2 6

a b s t r a c t

27

In this study, an investigation was conducted to explore and synthesize silicate (SiO2) glass from

28

29 [(ZnO)55+ (WRHA)45]100-X[MnO2]X, (where X = 0, 1, 3 and 5 wt%) was prepared by conventional melt

30 quenching technique The glass samples were characterized using energy dispersive X-ray fluorescence

31 (EDXRF), X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform

32 infrared (FTIR) spectroscopy, and ultraviolet–visible (UV–Vis) spectroscopy The results revealed that by

33 increasing the concentration of MnO2, the color of glass samples changed from colorless to brown and the

34 density of glass increased XRD results showed that a broad halo peak which centered on the low angle

35 (2h = 30°) indicated the amorphous nature of the glass FTIR results showed basic structural units of

36 Si-O-Si in non-bridging oxygen, Si-O and Mn-O in the glass network FESEM result showed a decreasing

37 porosity with an increasing MnO2content, which was attributed to the Mn ions resort to occupy

inter-38 stitial sites inside the pores of glass Besides, the absorption intensity of glass increased and the band

39 gap value decreased with increasing the MnO2percentage In this synthesized glass system of MnO2

40 doped zinc silicate glasses using RHA as a source of silica, the MnO2affect most of the properties of

41 the glass system under investigation

42

Ó 2017 Published by Elsevier B.V This is an open access article under the CC BY-NC-ND license (http://

43 creativecommons.org/licenses/by-nc-nd/4.0/)

44 45

46 Introduction

47 Rice husk (RH) is one of the agricultural waste materials that

48 received high attention because of its high amount of silica

con-49 tent Generally, in Malaysia for each 1000 kg of paddy milled,

50 220 kg (22%) of rice husk will be produced The subsequent

burn-51 ing of the rice husk will generate about 55 kg (25%) of rice husk

52 ash (RHA)[1] RHA have many good properties such as high

poros-53 ity, high external surface area, lightweight, and high in silica

con-54 tent inform of amorphous materials (87–97%) and a few metallic

55 impurities[2,3] Rice husk is an agricultural waste material that

56 is renewable and has low bulk density Unfortunately, this waste

57 is left to rot slowly in the field or burnt in an open space Many

sug-58 gest that recycling of the waste is the best way compared to these

59 unsafe disposals procedure several advantages such as resources

60 and energy saving, reduces incineration and helps in protecting

61

the environment[4–6] Nowadays, various researchers have done

62

many works toward utilizations of the waste materials in various

63

industries and as an additive in manufacturing some products

64 [7] Specifically, RHA had been used for development of advanced

65

materials and utilization in many areas Different processing

tech-66

niques and treatments were employed and effect of various

param-67

eters were studied [8,9] Currently, a considerable amount of

68

literature has been published on the use of glass in a wide range

69

of applications in many industries such as automotive, aerospace,

70

electrical, electronic and telecommunication Therefore, intensive

71

research has been carried out in order to improve the properties

72

of the glass, reduce the cost of the material and at the same lower

73

the fabrication cost These motivate researchers to developed new

74

fabrication techniques and utilization of waste materials for better

75

wealth and clean environment Therefore, the aforementioned

76

objectives could be achieved using RH, which is available and

77

abundant and will definitely lower the cost of final products

78

In 2011, Ruangtaweep and coworkers fabricate a glass using

79

55SiO2from RHA with the different formula of 20 Na2O, 13 B2O3,

80

6.3 CaO, 1.0 Al2O3, 0.2 Sb2O3, and 4.5 BaO by melt quenching

81

method at 1100°C The results of the study indicated that the

den-82

sity of glass derived from RHA is larger than pure SiO2 The results http://dx.doi.org/10.1016/j.rinp.2017.02.020

2211-3797/Ó 2017 Published by Elsevier B.V.

This is an open access article under the CC BY-NC-ND license ( http://creativecommons.org/licenses/by-nc-nd/4.0/ ).

⇑ Corresponding author at: Department of Physics, Faculty of Science, Universiti

Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia.

E-mail addresses: alnedaweali@yahoo.com (A.J.A Al-Nidawi), khamirul@upm.

edu.my (K.A Matori), azmizak@upm.edu.my (A Zakaria), mhmzaid@gmail.com (M.

H.M Zaid).

Contents lists available atScienceDirect

Results in Physics

j o u r n a l h o m e p a g e : w w w j o u r n a l s e l s e v i e r c o m / r e s u l t s - i n - p h y s i c s

Please cite this article in press as: Al-Nidawi AJA et al Effect of MnO doped on physical, structure and optical properties of zinc silicate glasses from waste

Trang 2

83 further confirmed that the RHA could be used for color glass

pro-84 duction[10] Insiripong et al (2013) synthesized a glass material

85 using high purity Na2CO3, B2O3, Al2O3, CaO, BaO, Sb2O3, and SiO2

86 from RHA In this research, the RH was sintered at 1000°C and

87 use as a SiO2source for glass production The physical properties

88

and the absorption peak were examined after doping RHA with

dif-89

ferent concentration of MnO2from 0.0 to 1.0 mol% The findings

90

revealed that the color of the glass changes from colorless to brown

91

by a gradual increase of MnO2 concentration Both density and

92

reflective index were also increased with the increasing of MnO2

93

concentration, largely, due to the altered atomic volume and an

94

atomic mass of the glass[11]

95

The focus of this study is to improve the properties of glasses

96

using white rice husk ash (WRHA) as a source of SiO2by preparing

97

zinc silicate glasses doped with MnO2using conventional melt and

98

quenching method The physical, structure and optical properties

99

of MnO2 doped zinc silicate glasses have been characterized to

100

study the effect of various concentrations of MnO2 on the glass

101

samples

102

Experimental work

103

Preparation of white rice husk ash

104

The rice husk used in this research was obtained from Tanjung

105

Karang, Selangor, Malaysia To prepare the white RHA, the husks

106

was thoroughly washed with tap water up to three times to

107

remove adhering soil and dust Later the husk was rinsed with

dis-108

tilled water to remove dirt and aqueous soluble substances by

109

repeated stirring and decanting until the aqueous wash turned

110

clear The cleaned RH was then dried in an oven at 100°C for

111

24 h The RH samples were later transferred into an electric furnace

112

for a double stage heating process at 500°C for 1 h and 900 °C for

113

3 h The burnt samples could cool to room temperature as seen in

114

the temperature cycle curve inFig 1

115

Preparation of ZnO-WRHA glasses

116

The pure powder of ZnO was mixed with WRHA The

117

mixture was doped with MnO2 in different ratio (X = 0, 1, 3,

118

and 5 wt%) ascribed to the empirical formula [(ZnO)55+

119

(WRHA)45]100-X[MnO2]X Dried milling process was carried out on

120

the mixture for 20 h to get homogenous powder Each batch of

121

the samples was placed in an alumina crucible and melted in an

122

electrical furnace at 1400°C for 2 h The melts samples were then

900 °C

500 °C

3 hours

1 hour

Room temperature

Time (Hours) Fig 1 Heating circle for burning rice husk.

Table 1 Chemical composition of WRHA.

Components Percentage by weight

p o s i t i o n ( 2 T h e t a )

S ( 2 0 0 )

S ( 1 0 1 )

S ( 1 1 1 )

S ( 1 0 2 )

S ( 2 0 2 )

S ( 2 1 2 )

S ( 3 0 1 )

S ( 3 0 2 )

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123 quenched in water to get glass frits After that, un-doped and

124 doped samples were crushed and ground to 63lm size powder

125 and compacted using a hydraulic press to get pellets of 13 mm

126 diameter and2 mm thick All the samples were stored in plastic

127 bags for further experimental investigations The density of the

128 glass samples was measured with electronic densitometer

MD-129 300S carried out at room temperature Other properties

investi-130 gated and analyzed using XRD, FTIR, FESEM, and UV–Visible

131 spectroscopy

132

Results and discussion

133

Characterization of WRHA

134

The chemical composition of WRHA sintered at 900°C for 3 h

135

was analyzed by (EDXRF) and the results are shown in Table 1

136

As seen in the table, the major constituent of WRHA is SiO2 at

137

94.34%, while other oxides (P2O5, K2O, CaO, Na2O, MgO, SO3,

138

Fe2O3,MnO, and ZnO) account for the remaining percentage This

Fig 3 FTIR result for WRHA.

2.85 2.9 2.95 3 3.05 3.1 3.15 3.2 3.25 3.3

3)

MnO2(wt.%)

(2.88)

(3.25)

Fig 4 Density of MnO 2 doped ZnO-WRHA glasses.

Please cite this article in press as: Al-Nidawi AJA et al Effect of MnO doped on physical, structure and optical properties of zinc silicate glasses from waste

Trang 4

139 result is consistent with previous studies which found the silica

140 contents in WRHA to be 94.3% and 92–97%[12,13]

141 The XRD analysis was done with PANalytical (Philips) X’ Pert

142 Pro PW3050/60 The XRD patterns of the sample are presented in

143 Fig 2 The pattern exhibits a sharp Bragg’s peaks at a low angle

144 region, which is apparent to the crystalline phase of silica after

145 RHA, have been heated to 900°C The figure also indicated different

146 peaks of crystalline components in the phase of cristobalite crystal

147 (SiO2) with the most intense peak at 22.049° and obviously, the

148 weak peaks at 28.451°, 31.543°, and 36.202°, respectively

149 The major chemical functional groups present in WRHA are

150 identified by the FTIR and the spectra are shows inFig 3 Looking

151 at the figure, the band at 3037.81 cm1was due to OH groups and

152 absorbed water [14] The predominant absorbance peak at

153 1606.66 cm1belonged to H-O-H bending vibration Besides, the

154 band at 1054.85 cm1 is assigned to the (Si-O-Si) asymmetry

155 stretching vibrations[15] Finally, there are two sharp bands at

156 783.22 and 441.85 cm1assigned to Si-O-Si symmetric stretching

157 and bending vibration respectively The results of the FTIR

con-158 firmed the presence of SiO2 in WRHA, which agreed well with

159 the XRD analysis

160 Properties of MnO2doped ZnO-WRHA glasses

161 Fig 4shows the density of ZnO-WRHA glasses at different

con-162 centration of MnO2(0, 1, 3 and 5 wt%) The results in the figure

163 showed that the density of the ZnO-WRHA glass increased from

164 2.885 to 3.253 g/cm3with increased of MnO2at 0, 1, 3 and 5 wt

165 % This increased in density is related to the atomic mass of Mn

166 (54.938 a.m.u) which is heavier when compared with other

ele-167 ments presence in the WRHA sample such as Si (28.086 a.m.u),

168 Na (22.989 a.m.u), and Ca (40.078 a.m.u)[16] In addition, other

169 researchers related this development to the figuration of the new

170 linkages inside the glass sample[17]

171 X-ray diffraction (XRD) patterns for all ZnO-WRHA glasses

sys-172 tem at various percentages of MnO2is shown inFig 5 From the

173 spectra, there is no strong sharp peak but one a broad halo peak

174 in the pattern of the un-doped and MnO2doped ZnO-WRHA based

175

glass samples The broad diffuse is around low angle 30° in entire

176

glasses samples, which reflected glass or amorphous nature of the

177

samples In addition, the glass under investigation has a long-range

178

structural disorder

179

The structure of all the glasses samples was determined with

180

the aid of FESEM as shown inFig 6 The results revealed the

pres-181

ence of fine pores on the ZnO-WRHA glass in an undoped sample

182

Despite the absence of a particular form of grain after doped, but in

183

general, the surface morphology shows a decrease in the number

184

of pores with increasing the percentage of MnO2 As seen in the

185

microstructural image of the samples prepared at different

per-186

centage of MnO2, the Mn resort to occupy interstitial sites within

187

the structure of the glass The lattice constant of glass increased

188

slightly with increasing concentration of MnO2, which leads to

189

increase of the degree of agglomeration that can be observed by

190

comparing the surface morphology inFig 6(a-d)[18]

191

The spectrums from FTIR results are shown inFig 7and it was

192

analyzed and compared with the relative information in the

liter-193

ature[19,20] The effective range of the spectrum observed from

194

400 to 1250 cm1, with the prominent band at 902.4 cm1ascribed

195

to Si-O-Si stretching in non-bridging oxygen[21] This peak

indi-196

cates the presence of SiO4in the sample The result from FTIR is

197

in good agreement with the result of XRD spectroscopy, which

198

revealed an amorphous phase for the entire glass samples On

199

the other hand, the peak at 1200–4000 cm1was clearly due to

200

the presence of water, hydroxyl, Si-OH or similar groups [22]

201

Therefore, the bands at 1555.85 could indicate Si-O or Mn-O, which

202

gives rise to an IR peak The peak at 3032.79 could be attributed

203

present H-bonding of H2O Furthermore, Zhang and Jahanshahi

204

suggests that this band might ascribe to absorb moisture from

205

the air[23]

206

The analysis of the optical absorption spectra is useful to locate

207

the width to the band gap in order to identify the substance from

208

the spectrum emitted or absorbance light in the material[24] The

209

optical absorbance of the MnO2 doped zinc silicate glasses is

210

shown inFig 8 As shown from the absorption curve, there is no

211

big sharp absorption edge, which dictates the presence glass phase

212

From the absorption curve, it can be observed that with increase of

0

1 0 0 0

2 0 0 0

3 0 0 0

4 0 0 0

5 0 0 0

P osition (2 T heta)

5 w t %

3 w t %

1 w t %

u n d o p e d

Fig 5 XRD pattern of MnO 2 doped ZnO-WRHA glasses.

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213 MnO2 concentration, the absorption intensity increased and

214 the intensive absorption, which can be seen in the range of

215 250–350 nm[25]

216 The optical band gap in the amorphous system is closely related

217 to the energy gap between the valence band and conduction band

218 In the amorphous system, the condition band affects by the new

219 glass formation anions The relation between absorption

coeffi-220

cient and extinction coefficient (K) in the equation below

determi-221

nes the experimental value of optical band gap:

222

225

From the plot of the extinction coefficient versus hv, the

exper-226

imental value for the optical band gap was extrapolating from the

227

linear region of the extinction coefficient (K) to zero After

Fig 6 FESEM image of MnO 2 doped ZnO-WRHA glasses, (a) undoped (b) 1 wt% (c) 3 wt% and (d) 5 wt%.

Please cite this article in press as: Al-Nidawi AJA et al Effect of MnO doped on physical, structure and optical properties of zinc silicate glasses from waste

Trang 6

228 compiled all the obtained Egvalues inTable 2, a good agreement

229 between the Egin the differential curve with the value in n = 3/2

230 can be observed Hence, the obtained experimental value of the

231 optical band gap arises in the glass system by direct forbidden

232 transitions The optical band gap value decreased from 4.70 to

233 4.21 with increasing the MnO2 percentage as can be seen in the

234 Fig 9 According to the literature review, with an increase in

235

MnO2in the glass network might lead to the breakdown of SiO4

236

network consequence to product non-bridging oxygen, whereby

237

the electrons were loosely bonded to NBO’s than BO’s[26]

238

Conclusions

239

A series of ZnO-WRHA glasses doped MnO2were prepared by

240

melt quenching technique with aim of studying the effect of

vari-241

ous concentration of MnO2on the physical, structure and optical

242

properties of the glass samples Upon density measurement by

243

Archimedes’ principle, the density increased from 2.885 to

244

3.253 g/cm3with increased in the percentage of MnO2from 0, 1,

245

3 and 5 wt% The XRD confirmed the formation of the amorphous

246

glassy phase in the samples The results from FTIR agreed with

247

the XRD pattern with a band at 902.4 cm1, which was attributed

248

to Si-O-Si stretching in non-bridging oxygen’s The FESEM images

249

shows decrease trend in the number of pores with increasing

per-250

centage of MnO2and glassy phase of samples From the absorption

251

curve, it can be observed with the increasing concentration of

252

MnO2, the absorption intensity increased and intensive absorption

253

can be seen in the range from 250 to 350 nm From the results of

254

the UV–visible spectroscopy, the optical band gap value decreased

Fig 7 FTIR spectra of MnO 2 doped ZnO-WRHA glasses.

0

0.2

0.4

0.6

0.8

1

1.2

wavelength (nm)

undoped

1 wt %

3 wt %

5 wt %

Fig 8 Absorption spectra of MnO 2 doped ZnO-WRHA glasses.

Table 2

Variation of Eopt for MnO 2 doped ZnO-WRHA glasses.

n = 2 in the indirect allowed transition 4.871 ± 0.03 4.42 ± 0.03 3.93 ± 0.03 3.93 ± 0.03

n = 3 in the indirect forbidden transition 4.08 ± 0.03 4.47 ± 0.03 3.41 ± 0.03 3.29 ± 0.03

n = 1/2 in the direct allowed transition 5.16 ± 0.03 5.14 ± 0.03 5.09 ± 0.03 5.05 ± 0.03

n = 3/2 in the direct forbidden transition 4.7 ± 0.03 4.61 ± 0.03 4.42 ± 0.03 4.21 ± 0.03

Trang 7

255 from 4.70 to 4.21 with increasing of MnO2percentage due to the

256 defect MnO2 in the samples and product non-bridging oxygen’s,

257 which leads to the breakdown of SiO4network

258 Acknowledgement

259 The authors gratefully acknowledge the financial support for

260 this study from the Malaysian Ministry of Higher Education

261 (MOHE) through the Fundamental Research Grant Scheme

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Please cite this article in press as: Al-Nidawi AJA et al Effect of MnO doped on physical, structure and optical properties of zinc silicate glasses from waste

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